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P. DANCKWARDT. PROCESS FOR THE PRODUCTION OF HYDHOCAHBONS 0F LOW BOILING POINTS FROM HYDHOCARBONS OF HIGH BOILING POINTS.

APPLICATION HLEU AUG.27. I917.

1,373,654. Patented Apr. 5, 1921.

I l I i J? E w E Z; E 23 I .i l a 21 49 22 ounce snags PATENT, calies.-

ram. nmcxwnmr, or DENVER, COLORADO. rnocnss son was rnonucrron or nrnaocnnnons or now BOILING-POINTS no! HYDBJOOLRBONS 0] HIGH BOILING-POINTS.

To all whom it may concern:

Be it known that I, Pam. DANOKWARM', a citizen of the United States, and a resident of Denver in the county of Denver and State of olorado, have invented certam new and useful Improvements in Processes for the Production of Hydrocarbons of L ow Boiling-Points from Hydrocarbons of High Boiling-Points, of which the following 18 a specification.

This invention relates to a rocess of chan ing the character of oils, suc as crude,

tro cum, petroleum products, tar and sinnar oils, with a view of obtaining more oils of relatively low boiling points from them than it is possible by present methods. It also comprises a method of improving the character of the oils thus. obtained in so far as to produce only, or nearly so, saturated hydrocarbons which can be sold directly to the consumer without subjecting them to further refining processes. More particularl stated, it comprises a process in which in t e presence of nickel in a finelyl divided state and a chlorid of nickel or anot er metal and a large percentage'of carbon, as con- I tact substances, the oil and aqueous fluid (that is to say, water or steam) are subjected to a heating process, thereby causing the oil to distil and combine with the hydrogen of the aqueous fluid and the hydrogen of hydrochloric acid formed during the process. It has long been known that nickel alone has the propert under certain conditions when steam an oil are passed over it, of causing the steam to split off its hydrogen and transfer this hydro n to the oil, in other words, to cause ad ition of hydrogen to the oil and render the oil lighter and more volatile. Soon however, it was discovered that the nicke when used for some time, would lose this property, mainly on account of sulfur and the oil combining with it. The recess therefore,has never come to be esta blished on a commercial scale.

The object of the present invention is to prevent such of the nickel and I obtain the desired result b adding a habit! of a metal, which under tlie conditions existing during the process will alternately formed. On account of their cheapne'ss I prefer to chlorids and nickel as the metal, though Specification 01' Letters Patent. Application and August av,

other impurities contained in deterioration of the qualities become decomposed and re-- use chloride, and preferably nickel Patented Apr.5, 1921. 191T. 8erial llo. 108,807.

other chloride will do metals. Instead of metallic nickel, I may employ nickel oxid or nickel carbonate.

e nickel is continually regenerated during the process by passing alternately into the form of nlckel chlori and becoming again reduced to the metallic state purities taken up as well, but not other while the imby it while it served as contact substance are driven out as volatile compounds. The other component of the chlorid, v1z., chlorin, combines with the h dro on of any aqueous fluid present, and t e so ormed l liydroehloricacid again produces chlorlds. is result is due to the decomposition occurring according to the formula,

' C+H,O=CO+H,, I

bly the action of the incandescent carbon of t e charge on the. aqueous fluid, the hydrogen thus liberated, combinin chlorin of the chlorids to form acid and metallic nickel.

similar to that described fication of equal date, Serial N 0. 188,305, but differs in so .far as here the hydro en of any aqueous fluid present within the c arge dur mg its treatment takes art directly inthe formation rocess of lig t hydrocarbons by addlng itse f directly under the catalyzing influence of metallic nickelto the heavier oils, as will be set forth more full hereinafter. Onl the reaction between tlie hydrochloric aci and any excess metal present is identical with the reaction made use of in my other application. In thisiprocess, not so much care need be taken to limit the supply of oxy on or air and all the heating may take 1p ace by the combustion of carbon (chic y the coke of the char with admission or injection (blast) o air to sup rt combustion. Instead of .air,'air enriche in oxygen or commercial oxygen may be em ployed. If air is ydrochloric Such a rocess is to 150 lbs. per square inch, but that is not absolutely necessary It accelerates the reaction, however, considerably.

Having briefly outlined my improved process, will proceed to describe the same in dated, and in so doing will explain a suit- 7 able apparatus for carrying out the same,

reference be drawing whic section.

In-this drawing; numeral 1 represents the had to the accompan represents a vertical cross with the.

used, the process becomes very cheap. I have employed pressures up in my 0t er speci- ,11. The lower compartment .9 is connected with a pipe ,6 leading into the top of the still are provided with valves 24: and 25 .bymea'ns of an elevator; shaft 12 containing vator 13, running on alleys and shafts 14 and 15, through-whic it is put into operation from-anoutside source .of power. The shell 12 is made. of steel, and so is the elevator a simple steel chain moving on sprocket wheels and carrying perforated steel buckets 16. Two or moretWyers 17 conve air under any amount. of pressure e interior of the still. They. have small. branch pi es with valves 32 to supply aqueous fluid say) steam. P1 is 7 rising from thetop of the still serves or the aurpose of conveying the gases and vapors rem the still to the container 18 consistingof a high steel cylinder closed at the bottom and to by plates 19 and 19 respectively. Another. '1 e 20 andpump: 21 connect the bottom 0. 1; soil container 18' with the interior of compartment 9.' A branch pipe 22 leads to a receptacle 23 andboth pipes 20 and 22 so that a supply may be drawn from either receptacle 23 .or'container'lB. Another pump 26 and ipe 27 establish means for passing fluid 20m compartment 9 to the container 18. A

. screen 28 fastened to an an le ring 29-29 allows only the oil and the. nor part of the charge to pass through ipe 27; The container 18 is provided wit outlet 30 for the vapors and gases formed, leadin them to a condenser (not shown) and wit a pipe 31 serving-for the supply offreshoil.

At. present the preferred form of apps- .ratus,.of a capacity of about 3,000 gallons of oil per twenty-four hours, when continuously operated, has the followin dimensions: The

still compartmentl hasa 'ameter of 3-} feet andaheight of 13 feet. The elevator pipe 12, in which the elevator 13 operates, is 15 inches in diameter and the container 18 is 15 feet'high' by '2 feet in diameter.

In order to operate mp process in the rst fill'the still 1 through the pipe 5 with the charge up to the level of the twyer 17. This charge is composed'of -85% carbon in the shape of a clean coke crushed to about the sizerof a nut; (which coke always contains some m0is- -ture,) 540% of nickelor nickel oxicl, and

5'10% of-oneor more chloride preferably nickel chlorid. On top of this c large at the level 02-17., I now place a small amount of wood shavings and ignite them through one of the twyers.- If valve 5 is open, enough draft is produced to set the wood alire. I now drop some charcoal through 5 upon the burning wood and when this is well ablaze, I pass air, or oxygen, or air enriched in oxygen, through 17 and through the charge, first under a light pressure, while filling graduall the still full of charge. I then close the vs vs of pipe 5 and raise the air pressure gradually, starting at the same time the elevator and the two pumps with valve 24 open and valve 25 closed the container having been filled previous with oil up to the middle. The effect of the blast on the combustion of the carbon (chiefly coke) is soon visible-in the heating of the oil in the coutainer 18, and the process is rapidly brought up to full action. At the twyer level, where the greatest heat exists, the nickel or other chlorid is decom )osed according; to the reaction expressed y the formula:

either through moisture in the charge or through aqueous fluid (say steam) admitted expressly for that purpose through pipes 32. 0 course if this aqueous fluid is in cctcd as water, it is almost immediately converted into steam. The hydrochloric acid thus liberated, together with excess steam and fixed ases are mostly forced upward and meet t e mixture of carbon and nickel and oil which is continually transported upward by the elevator from compartment 9, where a jet of oil pla *s on the charge coming down the shaft of the still. Thus the hydrochloric acid and steam react on the oil coming from above, through the intermediary of the nickel contained in the charge according to the general equations ui+sncl+o n =nion+c u and The oxygen probably reacts with carbon of the charge or carbon of the oil forming carbon monoxid. It ma also be that part of the H 0 is already ecom iosed at a lower level with the formation 0 CO and H and the hydrogen resulting from. this decomposition (according to the equation amp 3 the heavier part of the oil is liable to proceed farther down the shaft, "it will be more energeticall acted u 11 than that part of the 011 whic distils 0 already near the sur- 6 face of the charge, where the uses are more diluted in active matter. T e h drogenation, which forms an important eature of this process, is brought about by two factors: first, by purely chemical action exerted by the hydrogen liberated from hydrochloric acid, and second, by the catalytic action of nickel.

-*But the uplperhalf of the still is not the only place w are this hydrogenation process 15 is gomg on. The charge sinking below the twyer evelis all the time enriching itself in metallic Ni derived from the continued decomposition of the-chlorid, and when it reaches the outlet near 9, it is sprayed'with oil coming from container 18. Here then,

the same action occurs as on top though the catalytic reaction between nickel, steam carbon and oil probably prevails over the lpurely chemical reaction between nickel, ydirochloric acid and .oil. The wipers and gases here formed escape through t e elevator and down pipe 6 and are conveyed together with the top gases and vapors into the bottom of container 18. The pressure from the'blower 8 not shown) connected with the twyers 17 cross the mixture through the oil of the container. If not all the hydrochloric acid has been absorbed before it reaches the con-. tainer 18 it will here meet fresh fine charge coming through pipe 27 from the compartment 9. The purely chemical (substitution) reaction between hydrochloric acid, nickel and oil will, therefore, go on here to a considerable extent, but the catalytic reaction between nickel, steam carbon and oil undoubtedly will be weaker, unless the con tainer is at under pressure by roviding pipe 30 with a valve. I have foun that the .catal ic reaction mentioned above is accelerated y' an increase of pressure, but the substitution reaction between hydrocloric acid nickel, and oil does not appear to be aifected by pressure. In the preceding operation I have, however, only had in mind to work thestill proper under pressure, which is done by closing the valve in line 7 partly, until a pressure gage (not shown) placed 1n the line or on to of the.sti1l indicates-the proper degree. his pressure may va between 50 and 100 lbs. per square inch. orkin under such ressures, the temperature 0 the oil inthe Bottom of the still will be between 300 and 225? C. and that .of the oil in the bottom of the container 18 about 200 0., while the tem rature of the vapors in the up r part o the container 18 aduall'y fa to nearly 150 C. I operate t e blower all the time at such a speed as to maintain at the esca pifie 30 a temperature near 150 06 C. If s r e is observed, nothing but the lightest h drocarbons distil over, those of higher [M1 in points condensing 1n the u per part of t e container 18. Pump 21 will then return them to the system mixed with fresh oil flowi in through pi e 31. In working t is process wit compressed air a .considerable part of the coke in the charge will be' burnt ofi forming carbon monoxld. This would gradually decrease the amount of chargecontained 1D. the still in spite of some carbon being formed continually by-the oil coming in contact with very hot particles of charge, particularly at the lower end of the shaft. While, this should be avoided,it. cannot be avoided altoether, but the carbon thus formed benefits t e process in so far as it re lenishes part-at least of the burnt carbon. 'i o keep the total amount of charge contained in the apparatus and the roportion of carbon in thechar e as near y constant as possible, I run 1n through pump 21 whenever required, a mixture of oil and finely crushed carbon from receptacle 23 by opening valve 25 and closing temporarily valve 24. This ought to be done at re ular intervals to conform-with the rate 0 consumption of carbonof the charge.

As this process generates a large amount ed gases by burning part of the carbon to monox'id, the" rocess requires a c0mparativel large con enser. Even then it would be a visa le to place behind the condenser a scrubber containing cold crude oil and force all the fixed gases comin from the condenser through this oil, w ch will absorb the remaining gasolene and deliver as ractically free of gasolene. The era, e 011 enriched in hydrocarbons of relatively low boiling points is then fed into the container 18 instead of original crude oil, and the gasolene is thus recovered together with that of the process proper. Of course, another way of avoiding losses in gasolene, or cutting them down to the least possible amount would be, as mentioned above, by substitut ing for air, oxygen or air enriched in oxygen. This wou d reduce the bulkof fixed gases very much. At the same time, a waste as containing no .or little nitrogen, would e obtained, which has much greater value.

The amount of pressure to be used to conduct the process need in. no case exceed 150 lbs. per inch. I wish to emphasize, however, t at, it is not absolutely necessary to employ pressure at all, more than neces-- sary to overcome the resistance to the passage of the gases and vapors through the w ole system, though there exists no doubt, that pressure is of material assistance in ac- .celerati the reaction.

While in the a pended claims I have referred to nickel, desire it to be understood that this term is intended to cover the equivalents named in the specification, and simihydrocarbons o oi relatively'low boi larly, where I refer to nickel chlorid in the claims other chloride are to be considered as equivalents covered bysuch claims.

I claim:

1. The recess of producing hydrocarbons of relativel low'boiling points from hydrocarbons o relatively high boiling points, which consists ini iting a charge composed ef'a haIoid-salt, nickel, and a large percentage of carbon, keeping up combustion within'the charge bythe introduction of'a blast ,containing oxygen, passing simultaneously oil and aqueous fluid through the charge, and condensing the hydrocarbons of relatively 'lowboiling points separately from those of higher boiling points.

2. They recess of producing hydrocarbone of relativel low boiling points from hydrocarbons o "relatively high b01ling points, which consists in mix: a large percentage of carbon with a 'smal perccnta e of nickel chlorid' and nickel-,-1gnit1ngt e mixture" and blowing aira-ndsteam through it, bringing them posted the charge or mixturefro'm the point of greatest heat' to a pointofless heat where 'itis brought in contact withoilto be treated, distilling oil the oil under the influence of the contact substances and chemicals ofthe char e, and condensing the hydrocarbons of atively low boilin' points separately from those of higher bOl ing "points.

3. The ro'cessof producing hydrocarbone of relativcl low boiling points from f relatively high boiling points which consists in i ting a mixture ,of car on, niokelland nicke chl'orid, passing air andsteam' through the mixture to mai.ntain combustion, ad n ollto the mixture, allowin it to distil o passing it through another ody of oil and mixture ofthe above ingredients and condensing-that art of the oils w ich boils at or below 50 C. separatelyfrom the gorti on boiling at a temperature above sax point.

' 4. The process or reducing h mire-carbons ilpointa rom hydrocarbons of relatively 'gh' iJOlllIlg points, which consists in i nitin a charge conslsting of carbon,- a c orid 0 metal and nickel,

maintaining combustion by means of an air blast having" an admixture of steam, withdrawing-continually part of the charge be low the oint of entrance of the blast mixing-it wlth part of the oil to tree ,conveyin this new mixture eontmnell to the to o the char from which point it is al owecl to gra ually' descend toand past the point of entrance of the blast,-m1x1n'g 1t again with freshoil andre'peating the operation, all the time allowlng the oil vaoil to he treated in contact with the mixture in the area of moderate temperature, allowing the vapors formed by catalysis and through chemical reactions to escape to a proper condensing arrangement, where the y rocarbons of relatively low boiling points may be recovered separately from those of a higher boiling point.

6. The process of n'odu'cing gasolenc from crude oil or similar products, which consists in passing air and steam through a a burning mass of carbon, metal ch'lorid and metal, thereby clecom using at the point of highest temperature t e chlorid into its components, causing the chlorin to combine with ydrogen from the steam, forcing the gases to come in contact with portions of the charge less heated, where conditions for the reformation of the chlorid are favorable, introducing oil to be treated at such portions of the charge, thereby causing hydrogenat on of the oil to take place, passing the alterecl oil vapors through another body of oil containing more charge, and recovering the oils of relatively low boiling points separately from those of higher boiling points.

7. The process of reducing hydrocarbons of relatively low be ing points from hydrocarbons of relatively high boiling points, which consists in igniting a charge c0mposed of a chlorid, nickel, and a large percentage of carbon, and supporting its combustion with the aid of a blast containing oxygen, causing hydrogen in state mmccnd-i to reduce the chlorid, thus forming hydrochloric acid and metal, allowing the hydrochloric acid thus obtained, to react with said metal at a difierent portion of the material under treatment, thus producing hy drogen, passing simultaneously oil and an aqueous fluid through the charge, and condensing the hydrocarbons of relatively low boiling points separately from those of higher boiling points.

PAUL DANCKWARDT. 

